Precise control over the morphology and crystal structure of semiconductor-based optical materials is essential for optimizing their nonlinear optical properties. Morphological factors significantly affect the material’s interaction with light, influencing nonlinear absorption, harmonic generation, and optical confinement. In this study, the nonlinear optical (NLO) properties and optical limiting (OL) performance of bismuth vanadate (BiVO4) films depending on precursor solution pH condition, powder morphology and weight percentage of the BiVO4 powders in PMMA (10–30 wt.%) were investigated. The BiVO4 powders were synthesized via the hydrothermal method and the effect of precursor solution pH (pH of 1, 7.5 and 12) was investigated on the size and morphology of the BiVO4 powders. BiVO4 films were prepared using the spin coating method utilizing the BiVO4 powders and PMMA. The bandgap values of films were found to change from 3.39 to 3.56 eV depending on the BiVO4 growth solution pH. The nonlinear absorption coefficients (βeff), saturation intensity thresholds (ISAT) and optical limiting (OL) threshold were obtained using the open aperture (OA) Z-scan experiment. It has been observed that the nonlinear absorption and optical limitation performance of the BiVO4 films can be altered by changing the powder morphology and BiVO4 weight concentration. BiVO4 thin films fabricated using a precursor solution pH 12 and weight concentration of 30 wt.% showed the best performance among all fabricated films with the highest nonlinear absorption coefficient (βeff), saturation density threshold (ISAT) and lowest OL threshold value.